Apparatus for continuous catalysis



June 3, 2. I J. LIENHART 2,599,466

APPARATUS FOR CONTINUOUS CATALYSIS Original Filed June 27, 1946 2 SHEETS-SHEET l Jean n/zarz June 3, 1952 J. LIENHART 2,599,466

I APPARATUS FOR con'rmuous CATALYSIS Original Filed June 27, 1946 2 Sl-IEETS-Sl-XEET 2 Fig. 2.

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Patented 'June 3, 1952 APPARATUS FOR CONTINUOUS cA'rALYsIs' Jean 'Lien'hart, Paris, France, assignorfto Coin p'a'gnie Fran'caise De Raffinage, Paris, France,

a French corporation Original application June 2"7, .19 l'6, v Serial .No. 679,724. Divided and this application Aliglis t v19, 1948, Serial No. 45,157;

Claims. (01.234285) 1 Thepresent invention relates to an improved apparatus'forcarrying out a continuous catalytic reaction in the liquid phase. The present appa ratus has been found useful in the catalytic decarboxylation of rosin, and will be illustratively described in connection with this reaction although, as, the description proceeds, it will be apparent that the invention is applicable to many other types of catalytic reactions as well. The present applicatiojn'is' a division of my prior application Serial No. 679,724 filed June 27, 1946, now Patent-No. 2,517,690, dated August 8, 1950.

The catalytic decarboxylation of rosin has hitherto been carried out in boilers or stills of a capacity thatmay be as much as several tons. Suchb'oilerwwhich may or may not be provided with stirrers," contain-the mass of rosin to be deca'rboxylated and the catalyst, if one is used. Various catalysts have been proposed, including, for example, phosphoric acidin proportions which may vary; according to the authority, from r% to 50%; v

I have discovered that the decarboxylation of rosin may be carried out with advantage by feeding melted rosin into a liquid mass which contains the catalyst in solution or suspension, and which isin' a state'of violent agitation. The liquid mass usually, but not necessarily, comprises the decarboxylated oil itself, a part of whichis circulated in a closed circulating system from which a quantity of decarboxylatedoil corresponding to the rosin supplied is continuously removed,

'Ilie'cata-ly'st; which gradually becomes adulterat'ed with 'acid'tar's and thereby loses a part of its activity, is likewise continuously removed from the circulating'system, regenerated in any appropriate manner, and continuously or periodically reintroduced into the system. In this way the activity of the catalyst may be kept at a" good a'vera'gel'evel. Since the decarboxylated oil, on the-"on'ehand, and the catalyst and associated tars, on the other hand, form separate liquid phases, they may be efiectively separated by decahtation. Hence the reaction products, after gases and vapors have beenseparatedtherefrom, are subjected to continuous decant'ation in order to separate the oil from the acid tars formed, and-both tars andoil may be continuously removed from the system.

The objects andadvanta'ges 'of the present inylention may best be understood and appreciated by reference to the accompanying drawings .which'show. apparatus incorporating an illustrative embodiment :of the present invention and wherein-z In France May 8',

Figure 1 is a generaldiagrarnmatic view 'o'fithe apparatus for carrying out a continuousscatalytic reactionyand I Figure 2 is a vertical, axial sectionxthroughpthe decanter of Figure 1, showingusomewhat diagrammati'cal-ly the internal constructionof the decanter.

Referring firstto Figurell, the apparatusthere shown comprises a circulating-system including a vertical U-shapedcolumn E,.a .vaporseparator tank B,.a pipeA', a pumpA, ahdiniector ca As shown in thedrawing, the colummEidischarges into the tank B, and liquid from the .bottom of tank .13 flows throughpipe A :to ;the pump :A. whence .itflis ipumpe'dthrough injectorrC .to the weight- As previously described, thelpurnplA withdraws a liquid mixture .from. the bottom,-.oi tank B through thepipe A at asuitablerate,.sayJQO cubic meters per hour, and delivers it to;the .injector (2. The incoming melted resin from .tube D i d u e toa d orou l ixed. with th liquid reaction :masswhich; then passes into the column Within the column E are the haflies G which are so arranged asto keep the-liquid mass passing therethrough in a CQ IltiIlllQllS -;tafie of agitation, The desired agitation: may beeffected in various ways as, for example, byforaminous disks or conventional column packings.

In order to maintain thedesired.decarboxylation temperature in the columnar], which item perature when using the specificv catalyst disclosedherein, is of the order of, ;250 Cs the column is provided with an oil-circulation jacket 13' through. which hot oil can be circulated.

, Thecolumn Edischarges into the vapor separator tank B whereinliguidreaction productsv are separated, from gases and vapors which comprise decarboxylation products, such .ascarbondioxide, carbon monoxide, and hydrocarbons andalso water vapor and .pinoline. The gases and vapors collect in the dome F of the tank .13, and flow therefrom through :a dephlegmator Handsepa- 3 rator I, both of which are filled with a suitable packing such as Raschig rings. Entrained and condensed liquids from dephlegmator H flow directly back into tank B, whereas liquid separated in the separator I flows back to tank B through pipe R. The gases and vapors leave the apparatus through pipe S and fiow into a condenser and a pinoline and acid water separator (not shown). The tank B is provided with an oil circulation jacket B, by means of which a temperature of 250 C. is maintained therein and the reaction is completed within the tank.

Instead of using an injector such as the injector C, it is possible without departing from the invention to introduce the feed rosin ahead of the.

pump A in which case the desired agitation is effected inside the pump itself. However, the injector is preferably used owing to the fact that it produces very intimatemixing with a comparatively small expenditure of power.

Mounted within the separator tank B there is continuous decanter J described in more detail hereafter which serves to separate the decarboxylated oil from the catalyst and tars. The decanter J may have a volume of say 400 liters and makes it possible to remove, through pipe K, a decarboxylated oil that is practically free from catalyst. The catalyst and tars flow from decanter J downwardly through pipe Q to a T-shaped fitting V where they accumulate.

The mounting of decanter J within tank B offers several advantages. Thus the decanter acts as a core and reduces the efiective volume of the separator, thereby facilitating heat exchange from the heating medium in the jacket B to the liquid in tank B. Also, since the decanter is within tank B the decantation is effected in the hot state and at constant temperature.

The reference character L designates a pressure equalizing tube that equalizes the pressure between the top of the interior of decanter J and the interior of dome F of tank B. Also provided within tank B there is a float M which may be connected to suitable and well known apparatus (not shown) for regulating the removal of products from the circulating system.

The tars and the catalyst to be regenerated collect in the dead end of fitting V which thus comprises a collecting chamber or sump. Removal of collected liquid from the fitting V is effected through a-relatively small tube N by manipulation of valve N. The dead end fitting V obviates delicate adjustment of the flow rate of the removed tars since it enables more or less tar and catalyst to be removed from the system without the rate of removal being rigidly proportional to the output of the decanter.

Although any type of decanter i suitable for use in the present apparatus, the decanter shown in Figure 2 presents certain advantages in that it provides for decantation in a plurality of thin layers. Referring to Figure 2 the decanter there shown comprises an outer cylindrical shell or casing 10, an intermediate shell l2 and an inner shell 2. The intermediate shell l2 extends upwardly to a point somewhat below the top of the decanter, and the inner shell 2 extends downwardly from the top of the decanter to a point somewhat above the bottom of the decanter. The liquid mixture to be separated enters the bottom of shell through a hole [4, flows upwardly between shells IO and [2, then downwardly between shells l2 and 2 and into the central chamber of thedecanter. 7 l

Supported on the inner wall 2, there are a series of annular bafiles 3, 5 and I between and above which are mounted the trays 4, 6 and 8. As indicated by the arrows in Figure 2, the liquid flows through the hole in each annular battle and around the edge of each tray. The annular baffies 3, 5 and I slope downwardly toward their peripheries to provide a space in which the liquid mixture can accumulate and separate, and the shallow trays 4, B and 8 likewise provide a quiescent area for separation of the two liquid phases. The trays 4, 6 and 8 are provided respectively with the central down pipes l6, l8 and 20 through which the heavier liquid phase may flow downwardly and out through the discharge pipe Q of the decanter. Similarly, the annular baflles 3, 5 and 1 are provided with the peripheral down pipes 22, l and 24 respectively, through which the heavier liquid phase may flow toward the bottom of the decanter and eventually into discharge pipe Q. The space between shells l0 and I2 also communicates, near the bottom periphery of the decanter, with a branch of discharge pipe Q to permit the heavier liquid phase to flow therefrom into the discharge pipe.

Near the top of the decanter there is a discharge pipe K that extends through the side walls of the decanter and is provided with an inlet K confronting the top of the decanter. A pressure equalizing conection 26 in the top of the decanter communicates with the central chamber of the decanter and a second pressure equalizing connection 28 communicates with the space between shells l0 and I2.

As the liquid mixture flows upwardly through the decanter, separation is effected between the two liquid phases on the bafiles 3, 5 and I and the trays 4-, 6 and 8. The heavier liquid phase continuously flows downwardly through down pipes I6, I8 and 20 and 22, I and 24, whereas the lighter phase continues to rise through the decanter, and in separated condition fiows out of the decanter through pipe K.

From the foregoing description it is apparent that the present invention provides an unusually efiective apparatus for carrying out catalytic reactions in the liquid phase. The oil obtained by utilizing the present apparatus for the decalboxylation of rosin is of a fine color and requires less earth for refining orv isomerizing than the oils obtained by utilizing other apparatus.

Although the present apparatus has been described with reference to the decarboxylation of resin, it is manifestly-applicable to other continuous liquid phase catalytic reactions. In general, the apparatus of the invention may be used inany case where the finished product and/or the exhausted catalyst is separable from the circulating mass by decantation, or by-centrifugation.

Since many embodiments might bemade of the present invention and since many changes might be made in the embodiment disclosed herein, it isto be understood that the foregoing description is to be interpreted as illustrative only and not in a limiting sense.

I claim:

l. A combined liquid decanter and gas separator adapted for use in separating gaseous and two-phase liquid. materials which comprises a first outer substantially vertical closed vessel having an inlet aperture at' the top and side thereof whereby a mixture of gaseous and two liquid phases maybe conducted'into the first vessel; an outlet aperture at the 'top' of said vessel whereby disengaged gas may be conducted from said vessel; an outlet aperture at the bottom of the vessel whereby liquid may be discharged from said vessel; a second substantially vertical closed vessel within said first vessel; the top of said second vessel being below said inlet aperture; said second vessel having a plurality of side walls spaced alongside one another and thereby defining a path whereby entering liquid may flow first upwardly between the outermost side wall and that wall adjacent thereto and thence successively in generally reverse directions to the lower central portion of said second vessel; a substantially central inlet aperture in the bottom of said second vessel to permit entrance of liquid thereto; a plurality of vertically spaced trays and baflles within said second vessel to provide a sinuous path for ascending liquid and also defining quiescent zones therein; an outlet aperture in the upper portion of said second vessel for removing light separated liquid both from the first and second vessels and a plurality of conduits passing from uppermost to lowermost trays and bafiles respectively for discharging into a central outlet conduit in the bottom of the second vessel whereby heavier settled liquid may be discharged from the second vessel to a zone outside the first vessel.

2. A combined liquid decanter and gas separator adapted for separating gaseous and twophase liquid mixtures which comprises a first outer vessel which is substantially closed and vertically positioned; said first vessel having an inlet aperture at the upper side whereby said mixture may be introduced into the vessel; an inlet aperture at the top of said first vessel whereby disengaged gas may escape from said vessel; an outlet aperture at the bottom and approximately the center of the vessel whereby liquid may be discharged from said vessel; a second substantially vertical closed vessel within said first vessel; the top of said second vessel being below the inlet aperture of the first vessel; said second vessel having a substantially centrally positioned inlet aperture in the bottom thereof for the entrance of liquid to be sepa-,

rated; said second vessel having three adjacent side walls defining a path for said entering liquid whereby the entering liquid first flows upwardly between the outermost wall and the adjacent wall and thereupon flows downwardly to the central portion of the vessel between the middle wall and the innermost wall; a plurality of vertically spaced trays and bafiles within said second vessel to provide a sinuous path for ascending liquid and also providing quiescent zones on each tray and above each baflle whereby the liquid phases may settle in said quiescent zones; an outlet aperture in the upper portion of said second vessel which extends through the side Walls of said vessel and through the side wall of the first vessel for conducting light liquid material to a discharge zone; a plurality of conduits passing from tray to tray and from baflle to baflle to a central outlet conduit in the bottom of said second vessel whereby heavier liquid phases may be discharged to a zone outside the first vessel.

3. A combined liquid decanter and gas separator according to claim 2 wherein said second vessel contains at least two trays and at least two bailles.

4. A combined liquid decanter and gas separator according to claim 2 with the addition of a gas dephlegmator positioned over the gas outlet aperture of the first vessel.

5. A combined liquid decanter and gas separator according to claim 2 with the addition of a liquid level controller which maintains the level of liquid in the first vessel above the level of the uppermost discharge conduit of the second vessel.

JEAN LIENHART.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,934,309 Hoover Nov. 7, 1933 1,940,794 Fisher Dec. 26, 1933 2,283,209 Hull et al May 19, 1942 2,325,516 Holt et a1. July 27, 1943 2,332,527 Pyzel Oct. 26, 1943 2,374,511 Upham Apr. 24, 1945 

